EP1879548A2 - Process for coloring keratin fibers comprising metal complexes - Google Patents

Process for coloring keratin fibers comprising metal complexes

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Publication number
EP1879548A2
EP1879548A2 EP06754966A EP06754966A EP1879548A2 EP 1879548 A2 EP1879548 A2 EP 1879548A2 EP 06754966 A EP06754966 A EP 06754966A EP 06754966 A EP06754966 A EP 06754966A EP 1879548 A2 EP1879548 A2 EP 1879548A2
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EP
European Patent Office
Prior art keywords
unsubstituted
substituted
metal
alkyl
azo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06754966A
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German (de)
English (en)
French (fr)
Inventor
Nicole End
Kai-Uwe Schöning
Beate FRÖHLING
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BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Priority to EP06754966A priority Critical patent/EP1879548A2/en
Publication of EP1879548A2 publication Critical patent/EP1879548A2/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/496—Triazoles or their condensed derivatives, e.g. benzotriazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966—Triazines or their condensed derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/005—Disazomethine dyes
    • C09B55/006—Disazomethine dyes containing at least one heteroring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/58—Metal complex; Coordination compounds

Definitions

  • the present invention concerns coloring keratin fibers, especially human hair, with colored metal complexes.
  • a number of metal complexes containing multidental ligands have been known as catalysts for the oxidative coupling of hair dye precursors (DE-A-19852972; US-6648925). It has now been found that certain metal complexes may be used themselves with advantage as hair dyes.
  • the present invention relates to a non-oxidative process for coloring keratin fibers, which comprises contacting said fibers, with at least one colored metal-complex comprising a metal and a ligand of formulae (1), (2), (3), (4), (5) or (6)
  • Xi and X 2 are O, S or NR, wherein R is hydrogen; unsubstituted or substituted and/or interrupted or uninterrupted alkyl; unsubstituted or substituted aryl, heteroaryl, alkylsulphonyl or arylsulphonyl;
  • Ri and R 2 are independently of each other hydrogen; unsubstituted or substituted and/or interrupted or uninterrupted alkyl; unsubstituted or substituted and/or interrupted or uninterrupted cycloalkyl; unsubstituted or substituted aryl or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound;
  • R 3 and R 4 are independently of each other unsubstituted or substituted aryl or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound; R 5 , R 6 and R 7 are independently of each other unsubstituted or substituted aryl or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound; halogen; hydroxy;
  • R 8 and Rg are independently of each other unsubstituted or substituted and/or interrupted or uninterrupted alkyl or cycloalkyl; unsubstituted or substituted aryl or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound; or R 8 and R 9 , together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further heteroatoms; m is 0, 1, 2, 3 or 4; it being possible when a plurality of m is present to be selected independently of each other; n is 0, 1 , 2 or 3; it being possible when a plurality of n is present to be selected independently of each other; p is 0, 1 or 2; it being possible when a plurality of n is present to be selected independently of each other;
  • Z when present, is a substituent, it being possible when a plurality of substituents Z is present for those substituents to be selected independently of each other, with the proviso that a metal-complex of Fe 2+ with 2,4,6-tris-( ⁇ -pyridyl)-1,3,5-triazine, 1 ,10- phenanthroline or 4'-phenyl-2-2',2"-terpyridine is excluded.
  • the coloured metal complexes themselves act as the dyestuff, no additional dye is required in the present process for coloring keratin fibers, especially no dye precursor such as used in oxidative coupling reactions, e.g. aromatic phenols or aromatic amines which find use in the formation of oxidative hair colors. It is also not necessary to treat the keratine fibers with swelling agents (such as ammonia, which may cause unpleasant effects such as odor or skin irritation) beforehand to facilitate the migration of the dyes or dye precursors into the fibers.
  • swelling agents such as ammonia, which may cause unpleasant effects such as odor or skin irritation
  • the present process may advantageously be carried out in the absence of a keratine swelling agent; in a preferred process, the keratin fibers or the hair is contacted with the present colored metal-complex without pre-treatment or presence of a keratin swelling agent and without presence of a dye formed in an oxidative coupling reaction or a dye precursor for such a reaction.
  • the colored metal complexes have an extinction of at least 0.2, and more preferred of at least 0.4 in the wavelength range from 200 to 800 nm, preferably in the wavelength range from 400 to 700 nm.
  • the ligand of formula (1 ) - (6) itself may be coloured and/or colour may be generated or modified by the formation of a charge transfer complex with the metal atom.
  • the colored metal complex has an extinction coefficient of at least 1000 litre x mol 1 x c "1 in the wave length range from 200 to 800 nm, and preferably in the wavelength range from 400 to 700 nm.
  • the extinction and the extinction coefficient can be measured, for example, as given below: 100 mg ligand and 1 to 1.5 mol equivalent metal is mixed in 100 ml water.
  • 1 ml of the mixture is diluted with 10 ml water to form a sample, which is analyzed by the measuring instrument, Varian Cary 50 Scan, with a Xenon lamp.
  • the metal used in the present invention is, for example, a transition metal, such as a metal of the 4., 5., 6. or 7. periode of the periodic system of the elements.
  • a metal of the 4. periode is preferably manganese, iron, copper or zinc, or nickel, manganese, iron, copper.
  • the metal is iron or manganese, especially iron in the oxidation state Il or III and manganese in the oxidation states III to V are preferred. More preferred are iron in the oxidation state Il and the manganese in the oxidation state III. Most preferred is iron in the oxidation state II.
  • Dashed lines in formulae (1) and (3) indicate the optional presence of annellated aromatic or aliphatic 6-membered rings, which preferably are carbocyclic; for example, the compound of the formula (1) may conform to the formula
  • the metal complexes may have additional ligands, for filling up the co-ordination places of the metal, or bridging metal complexes with more than one metal.
  • Neutral ligands are for example monodonating base, such as ammonia, pyridine or water.
  • Anionic ligands are for example halide, nitro, nitrito, nitrate, thiol or thioalcoholate, CN " , SCN ' , acetate, trifluoracetate, formiate, carbonate, citrate, and perchlorate and complex anions, such as hexafluorophosphate.
  • oxo-ligands, peroxo-ligands or imino-ligands are possible.
  • These latter ligands are also suitable for bridging, forming polynuclearic metal complex compounds.
  • Polynuclearic metal complexes mean at least two metals in a metal complex compound. These at least two metals can have different or same oxidation states and/or be of the same or different group and period of the periodic system of the elements. Preferably, at least two metals are identically.
  • the metal complex may comprise also anionic counter ions for neutralizising the cationic metal complex compounds.
  • Preferred anionic counter ions are for example halide, especially chloride, chlorate, perchlorate, nitrate, hydroxide, complex anions, such as hexafluorophosphate, tetrafluoroborate, sulfate, anions of carbonic acids, such as formiate, acetate, benzoate or citrate.
  • halide especially chloride, chlorate, perchlorate, nitrate, hydroxide, complex anions, such as hexafluorophosphate, tetrafluoroborate, sulfate, anions of carbonic acids, such as formiate, acetate, benzoate or citrate.
  • the colored metal- complex comprises a metal and a ligand of formula (7)
  • Z and m are as defined as above.
  • the colored metal- complex comprises a metal and a ligand of formula (8)
  • the colored metal- complex comprises a metal and a ligand of formulae (9), (10), (11), (12), (13) or (14)
  • Z is defined as above, and m is 0 or 1 , and R is hydrogen; unsubstituted or substituted and/or interrupted or uninterrupted C r C 6 alkyl; unsubstituted or substituted phenyl; unsubstituted or substituted mesyl or tosyl.
  • the colored metal- complex comprises a metal and a ligand of formulae (15) or (16)
  • Ri and R 2 are independently of each other hydrogen; unsubstituted or substituted and/or interrupted or uninterrupted alkyl, preferably CrC 6 alkyl, more preferably methyl; unsubstituted or substituted and/or interrupted or uninterrupted cycloalkyl; unsubstituted or substituted phenyl or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound;
  • R 3 and R 4 are independently of each other unsubstituted or substituted ar ⁇ l or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound.
  • a substituent Z is unsubstituted or substituted and/or interrupted or uninterrupted alkyl or cycloalkyl; unsubstituted or substituted ar ⁇ l or heteroaryl; or unsubstituted or substituted radicals of azo or azomethine compounds; halide; cyano; guanidine; unsubstituted or substituted -OR 8 , -SR 8 , -0(CO)R 8 , -(CO)OR 8 , -NR 10 COR 8 , -CONR 10 , -OP(O)(OR 8 ) 2 , -P(O)(OR 8 ) 2 ,
  • R 8 , R 9 and R 10 are independently of each other hydrogen; unsubstituted or substituted and/or interrupted or uninterrupted alkyl, cycloalkyl, alkylen; unsubstituted or substituted aryl or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound; or R 8 and R 9 , together with the nitrogen atom linking them, forming an unsubstituted or substituted 5-, 6- or
  • aryl is unsubstituted or substituted C 5 -C 4o aryl, more preferred C 5 -C 2o aryl, most preferred unsubstituted or substituted phenyl, naphthyl, anthracenyl, fluorenyl or phenanthrenyl.
  • heteroaryl is unsubstituted or substituted acridinyl, benzimidazolyl; benzopyrazolyl; 1 ,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl; isoxazolyl; isoquinolinyl, phenanthrolinyl, terpyridinyl, triazolyl, oxazolyl, oxadiazolyl, thiadiazolyl, phenanthryl, phenazinyl, purinyl, pteridinyl, pyrazinyl, pyrazolyl, pyrimidinyl; pyridazinyl; pyridinyl; quinolinyl; thiophenyl; 1,3-thiazolyl; 1,2-thiazolyl; 1 ,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1 ,3,4
  • substitutents of alkyl, cycloalkyl or alkylene are unsubstituted or substituted aryl or heteroaryl; halide; hydroxy; thiol; nitro; sulfo; cyano; guanidine; -OR 8 , -SR 8 , -0(CO)R 8 , -(CO)OR 8 , -NR 10 COR 8 , - CONR 10 , -O-P(O)(OR 8 ) 2 , -P(O)(OR 8 J 2 , -OS(O) 2 R 8 , -S(O) 2 OR 8 , -S(O) 2 NR 8 R 9 , NR 8 R 9 or + NR 8 R 9 R 10 , wherein R 8 , R 9 and R 10 are independently of each other hydrogen; C r C 8 alkyl, unsubstituted or substituted aryl or heteroaryl; un
  • substitutents of aryl or heteroar ⁇ l are alky I, cycloalkyl; unsubstituted or substituted radicals of azo or azomethine compounds; halide; hydroxy; thiol; nitro; sulfo; cyano; guanidine; unsubstituted or substituted -OR 8 , -SR 8 , -0(CO)R 8 , -(CO)OR 8 , -NR 10 COR 8 , -CONR 10 , -O-P(O)(OR 8 ) 2 , - P(O)(ORs) 2 , -OS(O) 2 R 8 , -S(O) 2 OR 8 , -S(O) 2 NR 8 R 9 , NR 8 R 9 Or + NR 8 R 9 R 10 , wherein R 8 , R 9 and R 10 are independently of each other hydrogen; unsubstituted or
  • alkyl is for example CrC 18 alkyl, preferably CrC 6 alkyl, and more preferably CrC 4 alkyl
  • -S-alkyl is for example -S-C r C 18 alkyl, preferably -S-CrC 6 alkyl, and more preferably -S-C 1 -C 4 alkyl
  • -O-alkyl is for example -O-CrC 18 alkyl, preferably -O-CrC 6 alkyl, and more preferably -O-C r C 4 alkyl
  • alkylen is for example CrC 18 alkylene, preferably d-C 6 alkylene, and more preferably C r C 4 alkylene.
  • C r C 18 alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, I J' ⁇ '-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl, undecy, dodecyl, tredecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
  • C r C 6 alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl or n-hexyl.
  • CrC 4 alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • CrC 4 alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • Ci-C 6 alkylene is, for example, methylen, ethylen, propylen, isopropylen, n-butylen, sec- butylen, tert-butylen, n-pentylen, 2-pentylen, 3-pentylen, 2,2 1 -dimethylpropylen J cyclopentylen, cyclohexylen or n-hexylen.
  • Alkylsulphonyl is, for example, Ci-Ci 8 alkylsulphonyl, preferably CrC 6 alkylsulphonyl and more preferred d-C 4 alkylsulphonyl, which can be substituted, unsubstituted, interrupted or not interrupted, linear or branched, and preferably alkylsulphonyl is mesyl.
  • Alkyl or cycloalkyl generally is unsubstituted or substituted and/or uninterrupted or interrupted by, for example, interrupted by at least one heteroatom such as -O-, -S-, -(SO 2 )- or -(NR 10 )-, wherein R 10 has the above given definition.
  • Cycloalkyl may be mono, bi, tri or polycyclic.
  • Preferred cycloalkyl is C 5 -C 20 cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl.
  • Preferred interrupted cycloalkyl is the radical of pyrazol, oxazol, morpholino, piperidino, and piperazino.
  • Arylsulphonyl is, for example, unsubstituted or substituted C 5 -C 40 arylsulphonyl, more preferred C 5 -C 20 arylsulphonyl, and most preferred tosyl, naphthylsulphonyl, anthracenylsulphonyl, fluorenylsulphonyl or phenanthrenylsulphonyl, and especially most preferred is tosyl.
  • Azo or azomethine compounds each of them represent classes of dyes, which are, as for example, defined in the Color Index by the Society of Textile Chemist and Colorist. Any radical in the form of an azo or azomethine compound may be formed from one of these known dyes by abstraction of a hydrogen atom or an alkyl moiety such as a methyl group. Preferred are radicals which are unsubstituted azo or azomethine compounds. Preferred azo compound is Basic Orange 31 or Basic Red 51 and preferred azomethine compound is Basic Yellow 87.
  • Halogen is fluoro, chloro, bromo or iodide.
  • Preferred halogen is fluoro, chloro or bromo, and more preferred halogen is fluoro or chloro.
  • NR 8 R 9 is an amine , which is preferably a compound of formulae: -N(R 9 )-(C 1 -C 6 alkylene)-R 13J -N(R 9 )-(C 1 -C 6 alkylene)-NR 10 R 11 ; -N[(CrC ⁇ alkylene)-NRioRii]2; -N(R ⁇ )-(Ci-C ⁇ alkylene)-N e RioRiiRi2; -N[(Ci-C ⁇ alkylene)-
  • Rn and Ri 2 are each independently of the other hydrogen, CrCi 8 alkyl, aryl or heteroaryl, or Ri 0 and Rn, together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero- atoms; and
  • Ri 3 is OH, SH, -O-CrC 6 alkyl or-S-CrC 6 alkyl, aryl or heteroaryl.
  • More prefeferred are amines of formulae, -N(R 9 )-(Ci-C 6 alkylene)-Ri 3 , wherein Ri 3 is OH, SH, -O-CrC 6 alkyl or -S-CrC 6 alkyl, aryl or heteroaryl; and most prefeferred are amines of formulae:
  • amines of formulae -N(CH 3 )CH 2 CH 2 -OH; -NHCH 2 CH 2 -OH.
  • cyclic amines of formula NRi 0 Rn or NR 8 R 9 wherein Ri 0 and Rn or R 8 and R 9 , together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further heteroatoms, such as pyrazol, oxazol, morpholino, piperidino, piperazino.
  • cyclic amines of formulae Especially preferred are cyclic amines of formulae:
  • Examples of cations that come into consideration in the present invention include alkali metal cations, such as lithium, potassium, sodium and especially sodium, alkaline earth metal cations, such as magnesium and calcium, and ammonium cations.
  • alkali metal cations are preferred, especially sodium.
  • the present invention further concerns a metal complex comprising a metal and a ligand of formula (3a)
  • Xi, X 2 , Z and m are defined as given above, and a ligand of formula (6)
  • R 5 is unsubstituted or substituted heteroar ⁇ l or unsubstituted or substituted radical of an azo or azomethine compound; and R 6 and R 7 are independently of each other unsubstituted or substituted ar ⁇ l or heteroar ⁇ l; unsubstituted or substituted radical of an azo or azomethine compound; halogen; hydroxy; NR 8 R 9 , wherein R 8 and R 9 are independently of each other unsubstituted or substituted and/or interrupted or uninterrupted alkyl or cycloalkyl; unsubstituted or substituted aryl or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound; or R 8 and R 9 , together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further heteroatoms.
  • the present invention further concerns a ligand of formula (3a)
  • Xi, X 2 , Z and m are defined as given above, or a ligand of formula (6)
  • R 5 is 1 ,10-phenanthrolinyl; unsubstituted or substituted radical of an azo or azomethine compound; and R 6 and R 7 are independently of each other unsubstituted or substituted ar ⁇ l or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound; halogen; hydroxy; NR 8 R 9 , wherein R 8 and R 9 are independently of each other unsubstituted or substituted and/or interrupted or uninterrupted alkyl or cycloalkyl; unsubstituted or substituted ar ⁇ l or heteroaryl; unsubstituted or substituted radical of an azo or azomethine compound; or R 8 and R 9 , together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further heteroatoms.
  • the ligands of the present invention can be prepared in analogy to known processes.
  • the ligands of formula (1) can for example be prepared as given below: two parts of pyridine- 2-carboxylic acid ester and one part of acetone can be reacted with sodium hydride and the intermediate, a 1 , 3, 5-tri ketone, obtained after aqueous working-up can be reacted with ammonium acetate to synthesize the central pyridine ring. The corresponding pyridone derivatives are obtained, which can be converted into the chlorine compounds by reaction with a chlorinating agent, such as PCI 5 /POCI 3 .
  • a chlorinating agent such as PCI 5 /POCI 3 .
  • the ligand of formula (2) can be prepared for example in analogy to the synthesis of Skraup by contacting derivatives of o-phenylendiamine or derivatives of 8-aminochinoline with nitrobenzene in glycerine in the presence of concentrated sulphuric acid.
  • reaction is preferably carried out in a solvent, for example ethanol, by boiling for several hours under reflux.
  • Z and m are defined as given above for compound of formual (3).
  • the compounds of formula (4) can for example be prepared by a process comprising a) contacting a compound of formula (25)
  • Xi and X 2 are O, S or NR, wherein R is hydrogen; unsubstituted or substituted and/or interrupted or uninterrupted alkyl; unsubstituted or substituted aryl, heteroar ⁇ l, alkylsulphonyl or arylsulphonyl, with an amine of formula (26)
  • the compounds of formula (5) are for example usually prepared by condensation of mono- or dicarbonyl compounds with amines.
  • the compounds of formula (6) are for example usually prepared by substitution of trichlor- or trifluortriazine with a desired nucleophil.
  • the dyes of the invention are suitable for colouring keratin-containing fibres.
  • "Keratin- containing fibres” are to be understood as wool, furs, feathers and, especially, human hair.
  • the keratin-containing fibres may be pretreated. For example, hair may first be treated with a shampoo or peroxide.
  • the present invention concerns the use of at least one metal complex comprising a ligand selected from formulae (1), (2), (3), (4), (5) or (6) as defined above, and/or at least one ligand of formulae (3a), (4a) or (6a) as defined above for colouring keratinic fibers.
  • a further embodiment of the present invention concerns compositions comprising metal complexes according to the present invention, and/or at least one ligand according to the present invention.
  • the metal complex comprising a ligand selected from formulae (1), (2), (3), (4), (5) and (6) is present in the compositions according to the invention preferably in an amount of from 0.001 % to 5 %, especially from 0.01 % to 1 %, based on the total weight of the dyeing composition.
  • the complex may be formed by reacting an aqueous solution of a salt of a metal, especially a transition metal, with a solution of a ligand.
  • the solution of the metal salt and the solution of the ligand are applied to the keratin-containing fibres consecutively so as to form the complex in situ.
  • the sequence of addition does not effect the result.
  • the common anions which are used in the metal salts are for example chloride, iodide, perchlorate, fluoroborate, sulphate, nitrate, acetate, citrate, tartrate, high molecular weight sulphonates and sulphates, sulphite, high molecular weight carboxylate or nitritre; and preferably, chloride, sulphate, nitrateee, acetate, citrate, tartrate, sulphite, acids or nitrite are used.
  • Some oxidation states of metals used in the metal complexes are not stable in aqueous solutions. It may therefore be of advantage to form unstable oxidation states of metals in situ, just before the prepartion of the dyeing solution, by reduction or oxidation of more stable oxidation states of the metal.
  • iron in the oxidation state Il can be formed by reduction from iron in the oxidation state III.
  • Suitable reducing agents are for example ascorbic acid, glucose or alkali metal sulfites, such as sodium sulfite or potassium sulfite.
  • a buffer solution is a solution of a substance that minimizes changes in the pH when an acid or base is added to the solution and may for example contain alkali phosphates, citrates, acetates, or tris(hydroxymethyl)aminomethane salts.
  • Suitable agents for adjusting the pH of the solution of the metal complex or the ligand are ammonia, alkali hydroxide, alkali carbonates, organic bases such as amines or, if required, inorganic acids such as hydrochloric acid or organic acids such as citric acid.
  • the colouration of hair often is satisfactorily carried out at normal room temperature, i.e. in a temperature range of about 18 to 25°C, especially at about 20° C. Hair is suitably treated at a temperature conventionally used for the colouration of hair. Preferrably the temperature is less then 40° C. More preferably, the temperature is in the range of 20-30° C.
  • watermiscible solvents and solubilizers may be used such as alcohols, ketones, glycols, and non-ionic and amphoteric surfactive agents.
  • alcohols ketones, glycols, and non-ionic and amphoteric surfactive agents.
  • Typical examples are ethanol, n-propanol, isopropanol, n-butanol, isobutanol, dioxane, acetone, propylene glycol, polyethylene glycols, glycerol, sorbitol, polyoxyethylene sorbitans, polyoxyethylene phenols, betaine detergents, polyoxyethylene amines and ethoxylated lanolins.
  • the multiplicity of shades and the color fastness of the dyes used in accordance with the invention may be increased by combination with other non-oxidative dyes used in the field of hair-dyeing compositions, e.g. with direct dyes or nitro dyes; direct dyes may be cationic or uncharged.
  • the metal complex comprising a ligand selected from formula (1), (2), (3), (4),
  • (5) and/or (6) according to the invention may readily be used in combination with other dyes used in the colouring of hair such as • nitrobenzene derivatives, as described in WO 99/20235, especially page 26, line 7 to page 30, line 15,
  • • cationic dyes especially those described in particular on pages 11 to 27 of WO 95/01772. Especially suitable are Basic Yellow 87, Basic Orange 31 and/or Basic Red 51.
  • the dyeing compositions can usually be incorporated into an aqueous cosmetic carrier.
  • Suitable aqueous cosmetic carriers include, for example, creams, emulsions, gels and also surfactant-containing foaming solutions, e.g. shampoos or other preparations, that are suitable for use on keratin-containing fibres. Such forms of use are described in detail in Research Disclosure 42448 (March 1999). If necessary, it is also possible to incorporate the dyeing compositions into anhydrous carriers, as described, for example, in US-3 369 970, especially column 1 , line 70 to column 3, line 55.
  • the dyeing compositions according to the invention are also excellently suitable for the colouring method described in DE-A-3 829 870 using a colouring comb or a colouring brush.
  • the dyeing compositions according to the invention may furthermore comprise any active ingredient, additive or adjuvant known for such preparations.
  • the dyeing compositions in many cases comprise at least one surfactant. There are suitable in principle anionic and also zwitterionic, ampholytic, non-ionic and cationic surfactants. In many cases, however, it has proved advantageous to select the surfactants from anionic, zwitterionic and non-ionic surfactants.
  • the dyeing compositions of the invention usually contain the present metal complex in an amount from about 0.1 to about 5% by weight, preferably 0.2 to 2 % by weight, for example 0.1-0.9, or 1.1-2.0 % by weight of the composition or formulation.
  • Anionic surfactants suitable for use in the preparations according to the invention include all anionic surface-active substances that are suitable for use on the human body. Such substances are characterised by an anionic group that imparts water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately from 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and also hydroxy groups may be present in the molecule.
  • suitable anionic surfactants each in the form of sodium, potassium or ammonium salts or mono-, di- or tri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanol group:
  • acyl taurides having from 10 to 18 carbon atoms in the acyl group
  • - acyl isothionates having from 10 to 18 carbon atoms in the acyl group
  • esters of tartaric acid and citric acid with alcohols which are addition products of approximately from 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols having from 8 to 22 carbon atoms.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having from 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and also especially salts of saturated and especially unsaturated C 8 -C 22 car boxy lie acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
  • Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one -COO ( ) or -SO 3 ( ) group in the molecule are termed zwitterionic surfactants.
  • Zwitterionic surfactants that are especially suitable are the so-called betaines, such as the N-alkyl- N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl- dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethyl- hydroxyethylcarboxymethyl glycinate.
  • a preferred zwitterionic surfactant is the fatty
  • Ampholytic surfactants are to be understood as meaning surface-active compounds that, in addition to a C 8 -Ci 8 -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants include N-alkylglycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl- glycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having approximately from 8 to 18 carbon atoms in the alkyl group.
  • Ampholytic surfactants to which special preference is given are N-cocoalkyl- aminopropionate, cocoacylaminoethylaminopropionate and Ci 2 -Ci 8 acylsarcosine.
  • Non-ionic surfactants contain as the hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups.
  • Such compounds are, for example:
  • ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethyl- ammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethyl- ammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.
  • Further cationic surfactants that can be used in accordance with the invention are quatemised protein hydrolysates.
  • cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilised trimethylsilylamodimethicone), Dow Corning 929 emulsion (comprising a hydroxylamino- modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and also Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quatemium-80).
  • Alkylamidoannines especially fatty acid amidoamines, such as the stearylamidopropyl- dimethylamine obtainable under the name Tego Amid ® 18, are distinguished not only by a good conditioning action but also especially by their good biodegradability
  • estersquats such as the methyl hydroxyalkyl- dialkoyloxyalkylammonium methosulfates marketed under the trade mark Stepantex ® , are also very readily biodegradable.
  • quaternary sugar derivative that can be used as cationic surfactant is the commercial product Glucquat ® 100, according to CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride".
  • the alkyl-group-containing compounds used as surfactants may be single substances, but the use of natural raw materials of vegetable or animal origin is generally preferred in the preparation of such substances, with the result that the substance mixtures obtained have different alkyl chain lengths according to the particular starting material used.
  • the surfactants that are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of such addition products may either be products having a "normal” homologue distribution or products having a restricted homologue distribution.
  • "Normal” homologue distribution is to be understood as meaning mixtures of homologues obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts.
  • Restricted homologue distributions are obtained when, for example, hydrotalcites, alkali metal salts of ether carboxylic acids, alkali metal oxides, hydroxides or alcoholates are used as catalysts.
  • the use of products having restricted homologue distribution may be preferred.
  • - non-ionic polymers for example vinyl pyrrol idone/vinyl acrylate copopylmers, polyvinylpyrrolidone and vinylpyrrolidone/vinyl acetate copolymers and polysiloxanes
  • - cationic polymers such as quatemised cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, copolymers of dimethyldiallyl- ammonium chloride and acrylic acid, as available commercially under the name Merquat R 280 and the use of which in hair colouring is described, for example, in DE-A-4 421 031, especially page 2, lines 20 to 49, or EP-A-953 334, especially page 27, line 17 to page 30, line 11, acrylamide/dimethyldiallylammonium chloride copolymers, diethyl-sulfate- quatemised dimethylaminoeth
  • - zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium chloride/acrylate copolymers and octylacrylamide/- methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers,
  • - anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobomyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers, - thickeners, such as agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulose derivatives, e.g.
  • methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose starch fractions and derivatives, such amylose, amylopectin and dextrins, clays, e.g. bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, - structuring agents, such as glucose and maleic acid,
  • - hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin, and cephalins, silicone oils, and also conditioning compounds, for example such as those described in DE-A-19 729 080, especially page 2, lines 20 to 49, EP-A-834 303, especially page 2, line 18 to page 3, line 2, or EP-A-312 343, especially page 2, line 59 to page 3, line 11 ,
  • - protein hydrolysates especially elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolysates, condensation products thereof with fatty acids and also quatemised protein hydrolysates,
  • perfume oils dimethyl isosorbitol and cyclodextrins
  • solubilisers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol
  • anti-dandruff active ingredients such as piroctones, olamines and zinc Omadine
  • spermaceti such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
  • - swelling and penetration substances such as polyols and polyol ethers, as listed extensively, for example, in EP-A-962 219, especially page 27, lines 18 to 38, for example glycerol, propylene glycol, propylene glycol monoethyl ether, butyl glycol, benzyl alcohol, carbonates, hydrogen carbonates, guanidines, ureas and also primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole,
  • polyols and polyol ethers as listed extensively, for example, in EP-A-962 219, especially page 27, lines 18 to 38, for example glycerol, propylene glycol, propylene glycol monoethyl ether, butyl glycol, benzyl alcohol, carbonates, hydrogen carbonates, guanidines, ureas and also primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole,
  • - opacifiers such as latex
  • - pearlising agents such as ethylene glycol mono- and di-stearate
  • propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air, and also
  • constituents of the aqueous carrier are used in the preparation of the dyeing compositions according to the invention in the amounts customary for that purpose; for example emulsifiers are used in concentrations of from 0.5 to 30 % by weight and thickeners in concentrations of from 0.1 to 25 % by weight of the total dyeing composition.
  • the dyeing compositions are usually applied to the hair in an amount of from 10 to 100 g in the form of the aqueous cosmetic carrier, left there for approximately 30 minutes and then rinsed off or washed off with a commercially available hair shampoo.
  • a 12.5 mM solution is prepared by dissolving 38 mg 2-(methyl-[2,2';6'2"]terpyridine-4'yl- amino)-ethanol in 20 ml ethanol p. a..
  • a 60 mM solution is prepared by dissolving 1.6 g Fe(lll)-chlorid hexahydrate in 100 ml water. Preparing of the ascorbic acid solution (3):
  • a 60 mM solution is prepared by dissolving 1.06 g ascorbic acid in 100 ml water.
  • a blonde, a blonde bleached, a middle blonde and a bleached hair tress are treated in each case with 10 ml of the dyeing solution (4a) for 10 min. Afterwards the tresses are shampooed and dried on a glass plate. Result:
  • a 12.5 mM solution is prepared by dissolving 49 mg 1 ,10-phenanthrolin-5-ylamine in 20 ml ethanol p. a..
  • 300 ⁇ l ligand solution (1b), 60 ⁇ l Fe(lll)-solution (2) according to example 2, and 70 ⁇ l ascorbic acid solution (3) according to example 2 are mixed in 10 ml water.
  • a blonde, a blonde bleached, a middle blonde and a bleached hair tress are treated in each case with 10 ml of the dyeing solution (4b) for 45 min. Afterwards the tresses are shampooed and dried on a glass plate. Result:

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EP06754966A 2005-05-13 2006-05-03 Process for coloring keratin fibers comprising metal complexes Withdrawn EP1879548A2 (en)

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WO2009111611A2 (en) 2008-03-05 2009-09-11 Proteotech Inc. Compounds, compositions and methods for the treatment of islet amyloid polypeptide (iapp) accumulation in diabetes
CN102584686B (zh) * 2012-01-11 2014-02-12 淮海工学院 一种水溶性三联吡啶荧光化合物及其制备方法
PT3319959T (pt) 2015-07-06 2021-12-06 Alkermes Inc Inibidores hetero-halo de histona desacetilase
WO2017007755A1 (en) 2015-07-06 2017-01-12 Rodin Therapeutics, Inc. Heterobicyclic n-aminophenyl-amides as inhibitors of histone deacetylase
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FR3088200B1 (fr) * 2018-11-12 2021-02-26 Univ De Lorraine Utilisation d'un compose organometallique en tant qu'agent de demethylation de l'adn
CN120025548B (zh) * 2025-04-18 2025-07-08 杭州职业技术学院 一种可机洗真丝绸整理剂的制备方法及应用

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JPH07267952A (ja) * 1994-03-30 1995-10-17 Central Glass Co Ltd １，１０−フェナントロリン金属錯体エレクトロクロミック膜
DE19852972A1 (de) * 1998-11-17 2000-05-18 Henkel Kgaa Färbemittel mit Übergangsmetallkomplexen
DE19859681A1 (de) * 1998-12-23 2000-06-29 Henkel Kgaa Färbemittel mit Übergangsmetallen
JP2003128832A (ja) * 2001-10-23 2003-05-08 Inst Of Physical & Chemical Res 自己組織化有機薄膜を有する構造体
WO2004007657A1 (en) * 2002-07-11 2004-01-22 Ciba Specialty Chemicals Holding Inc. Use of metal complex compounds as oxidation catalysts
FR2869225B1 (fr) * 2004-04-22 2006-07-14 Oreal Composition pour la deformation permanente des cheveux contenant un reducteur et un photooxydant.

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